KR20180126027A - Pattern forming method, manufacturing method of substrate, optical component manufacturing method, circuit board manufacturing method, electronic component manufacturing method, and imprint mold manufacturing method - Google Patents

Abstract

A layer of a curable composition (A1) comprising a component (a1) as a polymerizable compound and a component (d1) as a solvent is laminated on the surface of a substrate and a component (a2) which is at least a polymerizable compound is coated on the layer of the curable composition (A1) and the curable composition (A2) are sandwiched between the mold and the substrate, and the light is irradiated to the mixed layer , And the mold is separated from the mixed layer after curing to form a pattern on the substrate.

Description

Pattern forming method, manufacturing method of substrate, optical component manufacturing method, circuit board manufacturing method, electronic component manufacturing method, and imprint mold manufacturing method

The present invention relates to a pattern forming method, a method of manufacturing a processed substrate, an optical component manufacturing method, a circuit board manufacturing method, an electronic component manufacturing method, and a manufacturing method of an imprint mold.

2. Description of the Related Art In semiconductor devices, MEMS and the like, there is a growing demand for miniaturization, and as a microfabrication technique, optical nanoimprint technology has attracted attention.

In a photo-nanoimprint technique, a photo-curable composition is cured in a state in which a mold having a fine concavo-convex pattern formed on its surface is pressed against a substrate (wafer) coated with a photo-curable composition (resist). Thus, the concavo-convex pattern of the mold is transferred to the cured film of the photo-curing composition to form a pattern on the substrate. According to the optical nanoimprint technique, a minute structure of several nanometers order can be formed on a substrate.

The optical nanoimprint technique described in Patent Document 1 will be described with reference to Figs. 1A to 1F. First, the liquid resist 102 is discretely dripped (patterning step (1), Figs. 1A to 1C) by using the ink jet method on the pattern formation area on the substrate 101. The droplet of the dropped resist 102 is poured on the substrate 101 as indicated by the arrow 104 indicating the direction in which the droplet spreads. This phenomenon is referred to as a free spread (Fig. 1C). Subsequently, the resist 102 is formed using a transparent mold 105 with respect to the irradiation light 106 to be described later on which a pattern is formed (mold contact process (2), Fig. 1 (d)). The droplet of the resist 102 spreads over the entire gap between the substrate 101 and the mold 105 as indicated by the arrow 104 indicating the direction in which the droplet spreads (Fig. 1D). This phenomenon is called spread. In the mold-contacting step, the resist 102 is also filled into the recesses on the mold 105 by capillary action as indicated by an arrow 104 indicating the direction in which the droplet spreads (see Fig. 1D) ). This charging phenomenon is called a " fill ". The time until the spread and fill are completed is called the charge time. After the filling of the resist 102 is completed, the resist 102 is cured by irradiating the irradiated light 106 (light irradiation step (3), Fig. 1E) (Mold-releasing step (4), Fig. 1F). By performing these processes, a photo-curing film 107 (FIG. 1F) having a predetermined pattern shape is formed on the substrate 101.

Japanese Patent No. 4791357

S. Reddy, R. T. Bonnecaze / Microelectronic Engineering, 82 (2005) 60-70 N. Imaishi / Int. J. Microgravity Sci. No.31 Supplement 2014 (S5-S12)

In the optical nanoimprint technique disclosed in Patent Document 1, there is a problem that throughput is low due to a long time (charging time) from the start of mold contact to the completion of spread and fill.

Therefore, the present inventors have devised a short-span time Nanoimprint Lithography (SST-NIL) with a short charge time, i.e., a high throughput. As shown in the schematic sectional views of Figs. 2A to 2G, the SST-

A first laminating step 1 (Figs. 2A and 2B) for laminating a liquid curable composition (A1) 202 on a substrate 201,

A second lamination step (2) (Figs. 2C and 2D) for discretely laminating droplets of the curable composition (A2) 203 onto the layer of the curable composition (A1)

(3) in which a mixed layer in which a curable composition (A1) 202 and a curable composition (A2) 203 are partially mixed is sandwiched between a mold 205 having a pattern and a substrate 201 2e),

A light irradiation step 4 (FIG. 2F) for curing the mixed layer by irradiating the light 205 from the mold 205 side,

A mold releasing step 5 (Fig. 2G) for separating the mold 205 having the pattern from the layer (cured film 207 having the pattern shape) containing the curable composition after curing,

.

In SST-NIL, a series of process steps from the second laminating step (2) to the mold-forming step (5) is referred to as "shot", and the mold 205 is formed of the curable compositions (A1) 203, that is, a region where a pattern is formed on the substrate 201 is referred to as a " shot region ".

In SST-NIL, the droplets of the curable composition (A2) 203 dropping discretely are dispersed in the liquid phase of the curable composition (A1) 202 as indicated by an arrow 204 indicating the direction in which the liquid droplets spread The charging time is short, and the throughput is high. The detailed mechanism of the SST-NIL will be described later.

The problems of the SST-NIL to be solved by the present invention will be explained using the schematic cross-sectional views of FIGS. 3A to 3D. The steps (1) to (3) in FIGS. 3A to 3C correspond to the second laminating step to the mold releasing step in FIGS. 2C to 2G, and the step (4) It corresponds to the lamination process.

The curable composition (A1) 302 is laminated on the substrate 301 over an area larger than the shot area, for example, the entire surface of the substrate 301, for example, by the spin coating method. On the other hand, the curable composition (A2) 303 is limited to the first shot area 304 and is discretely laminated using, for example, an inkjet method (step (1), FIG.

The atmosphere control base 307 is placed in the mold 308 in order to release oxygen which hinders the photo-curing by irradiating the irradiation light 306 over the mold contact process or the light irradiation process (process (2), Fig. 3B) And is sprayed from the periphery. At this time, the atmosphere control base 307 is also sprayed onto the curable composition (A1) 302 laminated outside the first shot area 304, such as the second shot area 305. [

Here, the droplet of the curable composition (A2) 303 dropped in the region 309 (the step (3), FIG. 3C) in which the atmosphere controlling body 307 is injected, among the adjacent second shot regions 305, (Step (4), Fig. 3d). That is, the inventors of the present invention have found a problem that a pattern can not be uniformly formed in the second shot area 305 due to the distribution of the droplet enlargement speed.

It is an object of the present invention to provide an SST-NIL technique which is high throughput and capable of forming a uniform pattern on a substrate.

A pattern forming method according to the present invention is a method for forming a pattern comprising a first laminating step of laminating a layer containing a curable composition (A1) containing at least a polymerizable compound (a1) and a solvent component (d1) One),

A second lamination step (2) in which droplets of the curable composition (A2) containing at least a polymerizable compound (a2) are discretely dripped and laminated on the layer containing the curable composition (A1)

(3) sandwiching a mixed layer in which the curable composition (A1) and the curable composition (A2) are partially mixed between a mold having a pattern and the substrate,

A light irradiation step (4) for curing the mixed layer by irradiating light from the mold side,

(5) for separating the mold from the cured mixed layer,

In a corresponding order,

The content of the component (d1) as a solvent in the curable composition (A1) is 90% by weight or more,

, The content of the component (d1) as a solvent in the curing composition (A1) in the second laminating step (2) is 10% by weight or less,

Wherein the surface tension of the component (d1) which is the solvent is lower than the surface tension of the composition of the component of the curable composition (A1) except for the component (d1)

.

According to the present invention, it is possible to provide a pattern forming method which is high in throughput and excellent in uniformity.

Other features of the present invention will become apparent from the following description, which illustrates various embodiments with reference to the accompanying drawings.

1A is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
1B is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
1C is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
FIG. 1D is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
1E is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
1F is a schematic cross-sectional view showing a prior art example of the optical nanoimprint technique.
2A is a schematic cross-sectional view showing an SST-NIL technique.
2B is a schematic cross-sectional view showing the SST-NIL technique.
2C is a schematic cross-sectional view showing the SST-NIL technique.
2D is a schematic cross-sectional view showing the SST-NIL technique.
2E is a schematic cross-sectional view showing the SST-NIL technique.
2F is a schematic cross-sectional view showing the SST-NIL technique.
2G is a schematic cross-sectional view showing the SST-NIL technique.
Fig. 3A is a schematic cross-sectional view for explaining a problem to be solved by the invention.
3B is a schematic cross-sectional view for explaining a problem to be solved by the invention.
3C is a schematic cross-sectional view for explaining a problem to be solved by the invention.
FIG. 3D is a schematic cross-sectional view for explaining a problem to be solved by the invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below. It is also within the scope of the present invention that modifications, improvements, and the like, as appropriate, are added to the embodiments described below based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. The component (a) contained in the curable composition (A1) is referred to as component (a1), and the component (a) contained in the curable composition (A2) is referred to as component (a2). The same applies to the components (b) to (d).

[Curable composition]

The curable composition (A1) of the present embodiment is a composition having at least a component (a1) which is a polymerizable compound and a component (d1) which is a solvent. The curable composition (A1) of the present embodiment may further contain a component (b1) which is a photopolymerization initiator and a component (c1) which is a non-polymerizable compound.

The curable composition (A2) of the present embodiment is a composition having a component (a2) which is at least a polymerizable compound. The curable composition (A2) of the present embodiment may further contain a component (b2) as a photopolymerization initiator, a component (c2) as a non-polymerizable compound, and a component (d2) as a solvent.

In this specification, the term "cured film" means a film obtained by curing a curable composition on a substrate. In addition, the shape of the cured film is not particularly limited, and the surface may have a pattern shape.

Hereinafter, each component will be described in detail.

<Component (a): Polymerizable compound>

Component (a) is a polymerizable compound. Herein, the polymerizable compound in the present specification is a compound which forms a film containing a polymer compound by a chain reaction (polymerization reaction) by reacting with polymerization factors (such as radicals) generated from the component (b) as a photopolymerization initiator.

As such a polymerizable compound, for example, a radical polymerizable compound can be mentioned. The component (a) which is a polymerizable compound may be composed of only one kind of polymerizable compound or may be composed of plural kinds of polymerizable compounds.

The radical polymerizing compound is preferably a compound having at least one acryloyl group or methacryloyl group, that is, a (meth) acrylic compound. Therefore, the curable composition according to the present embodiment preferably contains a (meth) acrylic compound as the component (a), more preferably the (meth) acrylic compound as the main component of the component (a) Most preferably all of them are (meth) acrylic compounds. Also, the main component of the component (a) described herein is a (meth) acrylic compound, which indicates that at least 90% by weight of the component (a) is a (meth) acrylic compound.

In the case where the radical polymerizing compound is composed of a plurality of compounds having at least one acryloyl group or methacryloyl group, it is preferable to include monofunctional (meth) acrylic monomers and polyfunctional (meth) acrylic monomers . This is because a cured film having a high mechanical strength can be obtained by combining a monofunctional (meth) acrylic monomer and a polyfunctional (meth) acrylic monomer.

Examples of monofunctional (meth) acrylic compounds having one acryloyl group or methacryloyl group include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxy (Meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (Meth) acrylate of EO-modified p-cumylphenol, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromo Modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl- (Meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl Acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, isobutyl (meth) acrylate, , Heptyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate, isodecyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, ethoxyethyleneglycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethyleneglycol (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like.

Molecules (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150 and M156 MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscot # 150, # 155, # 158, # 190, # 192, # 193, # 220, A, HOP-A, HOA-MPE, HOA-MPL, PO-A, DOP-A and DOP-A, 2100 and 2150 (manufactured by Osaka Yuki Kagaku Kogyo) R-128H (manufactured by Nippon Kayaku Co., Ltd.), NK (manufactured by Nippon Kayaku Co., Ltd.), P-200A, NP-4EA, NP-8EA, epoxy ester M- PHA, PHE-2, PHE-4, BR-31 and PHA-10G, AMP-10G and AMP-20G (all manufactured by Shin Nakamura Kagaku Kogyo K.K.), FA-511A, 512A and 513A But are not limited to, BR-31M, BR-32 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), VP (manufactured by BASF), ACMO, DMAA and DMAPAA

Examples of polyfunctional (meth) acrylic compounds having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethyl (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, , 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,3-adamantanedimethanol di (meth) acrylate, tris (2- (Meth) acrylates such as isocyanurate tri (meth) acrylate, tris (acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, dipentaerythritol penta Bis (4 - ((meth) acryloxy) phenyl) propane, PO-modified 2,2-bis ) Propane, EO, PO-modified 2,2-bis (4 - ((meth) acryloxy) phenyl) propane and the like.

As commercially available products of the above polyfunctional (meth) acrylic compound, Epimer (registered trademark) UV SA1002, SA2007 (manufactured by Mitsubishi Chemical), Viscot # 195, # 230, # 215, # 260, # 335HP, # 295, A, 9G-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (above, Kyoe Shagagaku), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA- M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (manufactured by Toagosei Co., Ltd.), Lipoxi (registered trademark) VR-77, VR-60 and VR-90 (manufactured by Showa Kogen Corporation) and the like.

Further, in the above-mentioned group of compounds, (meth) acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth) acryloyl group means a methacryloyl group having an acryloyl group or an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A refers to a compound in which a (meth) acrylic acid residue and an alcohol residue of Compound A are bonded through a block structure of an ethylene oxide group. PO represents a propylene oxide, and the PO-modified compound B refers to a compound in which a (meth) acrylic acid residue and an alcohol residue of the compound B are bonded through a block structure of a propylene oxide group.

The compounding ratio of the component (a1) which is a polymerizable compound in the curable composition (A1) is such that the total weight of the component (a1), the component (b1) and the component (c1) Is not less than 50% by weight and not more than 100% by weight based on the total weight of the components of the component (A1). Further, it is preferably 80 wt% or more and 100 wt% or less, more preferably 90 wt% or more and 100 wt% or less.

By setting the blending ratio of the component (a1) as the polymerizable compound in the curable composition (A1) to 50% by weight or more based on the total weight of the component (a1), the component (b1) and the component (c1) A cured film having a certain degree of mechanical strength can be obtained.

The compounding ratio of the component (a2) which is the polymerizable compound in the curing composition (A2) is such that the total weight of the component (a2), the component (b2) and the component (c2) Is not less than 50 wt% and not more than 99.9 wt% with respect to the total weight of the components of the component (A2). Further, it is preferably 80% by weight or more and 99% by weight or less, more preferably 90% by weight or more and 98% by weight or less.

By setting the blending ratio of the component (a2) which is a polymerizable compound in the curable composition (A2) to 50% by weight or more based on the total weight of the component (a2), the component (b2) and the component (c2) A cured film having a certain degree of mechanical strength can be obtained.

As will be described later, the curable composition (A1) preferably contains the component (d1), and the component (a1) preferably contains the component (d1) which is a solvent and the total weight of the components of the curable composition By weight or more and 0.01% by weight or more and 10% by weight or less.

&Lt; Component (b): Photopolymerization initiator >

Component (b) is a photopolymerization initiator.

In the present specification, the photopolymerization initiator is a compound which detects the light of a predetermined wavelength and generates the polymerization factor (radical). Specifically, the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (radiation such as charged particle beams of infrared rays, visible rays, ultraviolet rays, deep ultraviolet rays, X rays,

The component (b) may be composed of one kind of photopolymerization initiator or may be composed of plural kinds of photopolymerization initiators.

Examples of the radical generating agent include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole Dimeric dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer which may have a substituent of the formula: Benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'- diaminobenzophenone, 4-methoxy- Benzophenone derivatives such as' -dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone and 4,4'-diaminobenzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-l- - &lt; / RTI &gt; aminoaromatic ketone derivatives such as &lt; RTI ID = Dianthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di (tert-butylanthraquinone) 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone Quinones such as quinone; Benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin and propylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; Acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; Thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) Acylphosphine oxide derivatives such as phosphine oxide; Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde, 1- Oxazol-3-yl] -, 1- (O-acetyloxime); (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, and the like, but are not limited thereto.

As commercial products of the radical generators, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO , LR8893, LR8970 (manufactured by BASF), and Ubecryl P36 (manufactured by UCB), but are not limited thereto.

Among them, the component (b) is preferably an acylphosphine oxide-based polymerization initiator. In the above examples, the acylphosphine oxide-based polymerization initiator may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and other acylphosphine oxide compounds.

The blending ratio of the component (b) as the photopolymerization initiator in the curable compositions (A1) and (A2) is such that the total weight of the component (a), the component (b) ) Is 0.1 to 50% by weight based on the total weight of the components of the curable composition (A1) or (A2). Further, it is preferably 0.1 wt% or more and 20 wt% or less, and more preferably 1 wt% or more and 10 wt% or less.

By setting the compounding ratio of the component (b) to 0.1% by weight or more based on the total weight of the components (a), (b) and (c), the curing rate of the composition is increased and the reaction efficiency can be improved. When the blending ratio of the component (b) is 50% by weight or less based on the total weight of the components (a), (b) and (c), the cured film obtained is to be a cured film having a certain degree of mechanical strength .

<Component (c): Non-polymerizable compound>

The curable compositions (A1) and (A2) according to the present embodiment may contain, in addition to the above-described components (a) and (b) May further contain component (c). Examples of such a component (c) include a compound which does not have a polymerizable functional group such as a (meth) acryloyl group and does not have the ability to generate the polymerization factor (radical) by sensing light having a predetermined wavelength. For example, a sensitizer, a hydrogen donor, an internal release agent, a surfactant, an antioxidant, a polymer component, and other additives may be cited. As the component (c), a plurality of such compounds may be contained.

The sensitizer is a compound suitably added for the purpose of promoting the polymerization reaction and improving the conversion rate of the reaction. As sensitizers, for example, sensitizing dyes and the like can be mentioned.

The sensitizing dye is a compound which is excited by absorbing light of a specific wavelength and interacts with the component (b) which is a photopolymerization initiator. The interaction described here is energy transfer or electron transfer from the sensitizing dye in the excited state to the component (b) as the photopolymerization initiator.

Specific examples of the sensitizing dye include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, Based dye, a thiopyranium dye, a thiopyrilium dye, a melocyanine dye, a quinoline dye, a styrylquinoline dye, a ketokmarine dye, a thioxanthene dye, a xanthene dye, an oxolin dye, a cyanine dye, Based dye, a pyruvic salt-based pigment, and the like, but are not limited thereto.

The sensitizer may be used alone or in combination of two or more.

The hydrogen donor is a compound which reacts with an initiating radical generated from the component (b) which is a photopolymerization initiator or with a radical at the polymerization growing end to generate a more reactive radical. It is preferable to add the component (b) which is a photopolymerization initiator when it is a photo-radical generator.

Specific examples of such a hydrogen donor include n-butylamine, di-n-butylamine, allyl thiourea, triethylamine, triethylenetetramine, 4,4'-bis (dialkylamino) benzophenone, Amine compounds such as dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine and N-phenylglycine, 2-mercapto-N-phenylbenzoimidazole , Mercapto compounds such as mercaptopropionic ester, sulfur compounds such as s-benzylisothiuronium-p-toluenesulfinate, and phosphorus compounds such as tri-n-butylphosphine. Do not.

The hydrogen donor may be used alone or in combination of two or more. In addition, the hydrogen donor may have a function as a sensitizer.

An internal mold releasing agent may be added to the curable composition for the purpose of reducing the interfacial bonding force between the mold and the resist, that is, for reducing the releasing force in a mold-releasing step to be described later. As used herein, the term &quot; internal form &quot; means that the curable composition is added in advance to the curable composition prior to the placement process of the curable composition.

As the internal mold releasing agent, a surfactant such as a silicone surfactant, a fluorine surfactant, and a hydrocarbon surfactant can be used. Further, in the present invention, the internal mold release agent does not have polymerizability.

Examples of the fluorine-based surfactant include polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adduct of an alcohol having a perfluoroalkyl group, adduct of a perfluoropolyether polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) And the like. The fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, or the like in a part of the molecular structure (for example, terminal group).

As the fluorine-based surfactant, a commercially available product may be used. As commercial products, for example, Megapak (registered trademark) F-444, TF-2066, TF-2067, TF-2068 (manufactured by DIC), Fluorad FC-430 and FC- 431 (manufactured by Sumitomo 3M) EF-126, EF-127, MF-100 (manufactured by TOKEM PRODUCTS), PF-636 (trade name, , PF-6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions), Unidyne DS-401, DS-403, DS- 250), 251, 222F, and 208G (manufactured by Neos Co., Ltd.).

The internal release agent may be a hydrocarbon-based surfactant.

Examples of the hydrocarbon surfactants include alkyl alcohol polyalkylene oxide adducts in which an alkylene oxide having 2 to 4 carbon atoms is added to an alkyl alcohol having 1 to 50 carbon atoms.

Examples of the alkyl alcohol polyalkylene oxide adducts include methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol Ethylene oxide / propylene oxide adducts and the like. The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group which can be produced by simply adding a polyalkylene oxide to an alkyl alcohol. The hydroxyl group may be substituted with a hydrophobic functional group such as a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group or a silanol group, an alkyl group or an alkoxy group.

Commercially available alkyl alcohol polyalkylene oxide adducts may be used. Examples of commercially available products include polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Yushi Co., Ltd., polyoxyethylene decyl ether (FINESURF D-1303, D-1305, D-1307, D-1310), polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) manufactured by Aoki Yushi Co., Ltd. (BLAUNON EL- 1505), polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Yushi Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct Water) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), randomly polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA- 50/50 1000R, SA-30/70 2000R), polyoxyethylene methyl Terminus (Pluriol (TM) A760E), polyoxyethylene alkyl ether of claim Gao (meolgen series) and the like.

Among these hydrocarbon surfactants, the internal release agent is preferably an alkyl alcohol polyalkylene oxide adduct, more preferably a long chain alkyl alcohol polyalkylene oxide adduct.

One type of the internal mold release agent may be used alone, or two or more types may be used in combination.

The blending ratio of the component (c) as the non-polymer compound to the curable composition (A1) and the component (A2) is such that the total weight of the component (a), the component (b) (C) is 0% by weight or more and 50% by weight or less based on the total weight of the components of the curable compositions (A1) and (A2). Further, it is preferably 0.1 wt% or more and 50 wt% or less, and more preferably 0.1 wt% or more and 20 wt% or less.

By setting the blending ratio of the component (c) to 50 wt% or less based on the total weight of the components (a), (b) and (c), the resulting cured film can be a cured film having a certain degree of mechanical strength .

&Lt; Component (d): Solvent >

The curable composition (A1) of the present embodiment contains a component (d1) which is a solvent. This is because the spin coating method is preferable as a coating method of the curable composition (A1) on a substrate as described later. In order to form a pattern of 1 nm or more and 100 nm or less by the photo-nanoimprint method of the present invention, the film thickness of the curable composition (A1) is preferably about 1 nm or more and 100 nm or less. Therefore, the content of the component (d1) as a solvent in the curable composition (A1) is preferably 90 wt% or more and 99.99 wt% or less, particularly preferably 99 wt% or more and 99.9 wt% or less. As the component (d1) which is the solvent of the curable composition (A1), the component (a1), the component (b1) and the component (c1) A solvent having a lower surface tension than the composition of the components of the curable composition (A1) except for the component (d1) which is a solvent is used. The lower the surface tension of the component (d1) which is the solvent, the more uniform the film is obtained by the spin coating method. A more preferred solvent is a solvent having a boiling point at normal pressure of 80 占 폚 to 200 占 폚. More preferably, it is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group and an ether structure. Specific examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone,? -Butyrolactone, ethyl lactate, or a mixture containing at least one of these Solvent.

The curable composition (A2) of the present embodiment may also contain a component (d2) which is a solvent. The component (d2) to be added to the curable composition (A2) is not particularly limited as long as it is a solvent in which the component (a2), the component (b2) and the component (c2) are dissolved. A preferable solvent is a solvent having a boiling point at normal pressure of 80 占 폚 to 200 占 폚. More preferably, it is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group and an ether structure. Specific examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, 2-heptanone,? -Butyrolactone, ethyl lactate, or a mixture containing at least one of these Solvent.

&Lt; Temperature during compounding of curable composition >

In the production of the curable compositions (A1) and (A2) of the present embodiment, each component is mixed and dissolved under a predetermined temperature condition. Concretely, it is performed in a range of 0 ° C or more and 100 ° C or less.

&Lt; Viscosity of Curable Composition >

The curable compositions (A1) and (A2) of the present embodiment are preferably liquid. This is because the spreading and filling of the curable composition A1 and / or A2 is completed quickly, that is, the charging time is short in the mold contact process described below.

The viscosity of the composition of the component of the curable composition (A1) other than the component (d1) which is the solvent in the present embodiment at 25 占 폚 is preferably 1 mPa 占 퐏 or more and 1000 mPa 占 퐏 or less. More preferably 1 mPa 占 퐏 or more and 500 mPa 占 퐏 or less, and still more preferably 1 mPa 占 퐏 or more and 100 mPa 占 퐏 or less.

The viscosity of the composition of the component of the curable composition (A2) other than the component (d2) which is the solvent in the present embodiment at 25 占 폚 is preferably 1 mPa 占 퐏 or more and 100 mPa 占 퐏 or less. More preferably 1 mPa 占 퐏 or more and 50 mPa 占 퐏 or less, and still more preferably 1 mPa 占 퐏 or more and 12 mPa 占 퐏 or less.

By setting the viscosities of the curable compositions (A1) and (A2) to 100 mPa 占 퐏 or less, the spreads and peels are completed quickly when the curable compositions (A1) and (A2) are brought into contact with the mold (Non-Patent Document 1). That is, by using the curable composition according to the present embodiment, the optical nanoimprint method can be performed with high throughput. In addition, pattern defects due to poor charging are unlikely to occur.

When the viscosity is 1 mPa s or more, uneven coating is less likely to occur when the curable compositions (A1) and (A2) are coated on a substrate. Further, when the curable compositions (A1) and (A2) are brought into contact with the mold, the curable compositions (A1) and (A2) are difficult to flow out from the ends of the mold.

&Lt; Surface tension of curable composition >

In the curable compositions (A1) and (A2) of the present embodiment, the surface tension of the composition of the components of the curable compositions (A1) and (A2) other than the component (d) being a solvent at 23 캜 is preferably 5 mN / m Or more and 70 mN / m or less. It is more preferably 7 mN / m or more and 50 mN / m or less, and still more preferably 10 mN / m or more and 40 mN / m or less. Here, when the surface tension is higher, for example, 5 mN / m or more, the capillary force acts strongly, so that when the curable composition A1 and / or A2 is brought into contact with the mold, charging (spreading and peeling) And is completed in a short time (non-patent document 1).

By setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition becomes a cured film having surface smoothness.

In the present embodiment, the surface tension of the composition of the component of the curable composition (A1) other than the component (d1) which is the solvent is higher than the surface tension of the composition of the component of the curable composition (A2) . The free spread of the curable composition A2 is accelerated (the droplet spreads widely) due to the effect of the marangoni to be described later, so that the time required for the spread in the mold-contacting step to be described later is shortened, Is shortened.

The Marangoni effect is a phenomenon of free surface movement due to the local difference in the surface tension of the liquid (Non-Patent Document 2). Using a difference in surface tension, that is, a difference in surface energy, as a driving force, diffusion occurs in which a liquid having a low surface tension covers a wider surface. That is, when the curable composition (A1) having a high surface tension is applied to the entire surface of the substrate and the curable composition (A2) having a low surface tension is dropped, the free spread of the curable composition (A2) is accelerated. When the curable composition (A2) is dropped onto the film of the curable composition (A1), the surface tension of the film of the curable composition (A1) is preferably 2 mN / m or more higher than the surface tension of the curable composition (A2).

Here, the inventors of the present invention have found that the component (d1) which is a solvent remaining in the film of the applied curable composition (A1) greatly affects the Marangoni effect. As described above, for the component (d1) which is the solvent of the present invention, a solvent having a low surface tension is used for spin coat uniformity. If the component (d1) which is a solvent remains in the film of the curable composition (A1), the surface tension of the film is low and the effect of the marangoni is not fully manifested.

When the atmosphere control body 307 is sprayed as shown in Fig. 3B in a state where the solvent d1 as the solvent remains, the volatilization of the solvent d1 as the solvent is promoted in the region. The surface tension of the film of the curable composition A1 is increased by the volatilization of the component (d1) which is a solvent having a low surface tension, and the marangoni effect is strongly exhibited. That is, in the second shot area 305 of FIG. 3A, a portion having a strong Marangoni effect and a weak portion are generated, and the uniformity of pattern formation is impaired.

On the basis of the above view, the present inventors reached the conclusion that the remaining solvent (d1) in the applied curable composition (A1) should be kept in advance. According to the present invention, the difference in the marangoney effect between the region where the atmosphere control body 307 is sprayed and the region where the atmosphere control agent 307 is not sprayed is small and a uniform pattern can be formed.

&Lt; Contact angle of the curable composition &

The contact angles of the curable compositions (A1) and (A2) according to the present embodiment are set such that the composition of the components of the curable compositions (A1) and (A2) except for the component (d) Is preferably from 0 DEG to 90 DEG. If the contact angle is larger than 90 DEG, the capillary force acts in the negative direction (direction in which the contact interface between the mold and the curable composition contracts) in the inside of the mold pattern or the gap between the substrate and the mold, and is not charged. And it is particularly preferable that the angle is not less than 0 DEG and not more than 30 DEG. The lower the contact angle is, the stronger the capillary force is, so the charging speed is faster (Non-Patent Document 1).

The viscosity, surface tension and contact angle of the curable compositions (A1) and (A2) according to the present embodiment can be changed by adding the component (d) as a solvent, but the component (d) as a solvent interferes with the curing of the curable composition do. Therefore, in the present embodiment, it is preferable to set the viscosity, surface tension, and contact angle of the composition of the components of the curable compositions (A1) and (A2) other than the component (d) being a solvent to a predetermined value.

&Lt; Impurities mixed in the curable composition >

It is preferable that the curable compositions (A1) and (A2) of this embodiment contain as little impurities as possible. The impurities described here mean those other than the above-mentioned components (a), (b), (c) and (d).

Therefore, the curable composition according to the present embodiment is preferably one obtained through a purification process. Such a purification process is preferably filtration using a filter or the like.

The filtration using the filter is carried out by mixing the above-mentioned components (a), (b) and additives to be added as required, and then filtrating them with a filter having a pore diameter of 0.001 to 5.0 m . When filtration using a filter is performed, it is more preferable to perform filtration in multiple stages or to repeat filtration many times. Further, the filtrate may be filtered again. It may be filtered using a plurality of filters having different hole diameters. As the filter used for filtration, a filter made of a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like can be used, but it is not particularly limited.

By such a purification step, impurities such as particles incorporated in the curable composition can be removed. Thereby, impurities such as particles can inadvertently cause irregularities in the cured film obtained after curing the curable composition, thereby preventing occurrence of defects in the pattern.

In the case where the curable composition according to the present embodiment is used for manufacturing a semiconductor integrated circuit, the incorporation of impurities (metal impurities) containing metal atoms in the curable composition is minimized so as not to hinder the operation of the product It is desirable to avoid. In this case, the concentration of the metal impurity contained in the curable composition is preferably 10 ppm or less, more preferably 100 ppb or less.

[Pattern formation method]

Next, the pattern forming method according to the present embodiment will be described using the schematic sectional views of Figs. 2A to 2G.

The pattern forming method according to the present embodiment is a form of the optical nanoimprint method. In the pattern forming method of the present embodiment,

A first lamination step (1) of laminating the above-described curable composition (A1) 202 of the present embodiment on a substrate 201,

A second lamination step (2) of laminating the curable composition (A2) 203 on the layer of the curable composition (A1) 202,

(3) sandwiching a mixed layer in which a curable composition (A1) 202 and a curable composition (A2) 203 are partially mixed between a mold (205) having a pattern and a substrate (201)

A light irradiation step (4) of curing the mixed layer by irradiating the irradiation light (206) from the mold (205) side,

(5) for separating the mold (205) from the cured film (207) containing the curable composition after curing,

.

The cured film obtained by the process for producing a patterned cured film according to the present embodiment is preferably a film having a pattern of a size of 1 nm or more and 10 mm or less. It is more preferable that the film has a pattern of a size of 10 nm or more and 100 占 퐉 or less. Generally, a pattern forming technique for producing a film having a nano-size (1 nm or more and 100 nm or less) pattern (concavo-convex structure) using light is called a photo-nanoimprint method. The pattern forming method according to the present embodiment uses a photo-nanoimprint method.

Hereinafter, each process will be described.

&Lt; First lamination step (1) >

2A and 2B, the curable composition (A1) 202 according to the present embodiment described above is laminated (coated) on a substrate 201 to form a coating film .

The substrate 201 on which the curable composition (A1) 202 is disposed is a substrate to be processed, and a silicon wafer is usually used. A processed layer may be formed on the substrate 201. Another layer may be formed between the substrate 201 and the processed layer. Further, when a quartz substrate is used as the substrate 201, a replica (mold replica) of a quartz imprint mold can be manufactured.

However, in the present invention, the substrate 201 is not limited to a silicon wafer or a quartz substrate. The substrate 201 may be arbitrarily selected from those known as substrates for semiconductor devices such as aluminum, a titanium-tungsten alloy, an aluminum-silicon alloy, an aluminum-copper-silicon alloy, silicon oxide, silicon nitride and the like.

The surface of the substrate 201 (substrate to be processed) or the work layer to be used is subjected to surface treatment such as silane coupling treatment, silazane treatment or film formation of an organic thin film to form the curable compositions A1 and 202 A2) 203 may be improved.

Examples of the method for disposing the curable composition (A1) 202 on the substrate 201 or the working layer in the present embodiment include an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, A gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or the like can be used. In the present invention, the spin-coat method is particularly preferable.

In the present invention, when the curable composition (A1) 202 is disposed on the substrate 201 or the work layer, the content of the component (d1) as a solvent in the curable composition (A1) Or less. To this end, it is preferable to carry out a baking step as needed to volatilize the component (d1) which is a solvent. Further, it is preferable that the component (a1), the component (b1) and the component (c1) have low volatility so as not to be volatilized in the baking step.

The baking process can be performed by a known method such as an oven or a hot plate. The baking can be performed at 30 to 200 DEG C for 1 to 600 seconds. It is preferable to appropriately set the conditions so that the component (a1), the component (b1), and the component (c1) are not volatilized while the component (d1) which is the solvent is volatilized.

The average film thickness of the film of the curable composition (A1) 202 varies depending on the intended use, but is, for example, from 0.1 nm to 10,000 nm, preferably from 1 nm to 20 nm, 1 nm or more and 10 nm or less.

&Lt; Second lamination step (2) >

In this step (second laminating step), droplets of the curable composition (A2) 203 are dispersed dropwise onto the layer of the curable composition (A1) 202 as shown in Fig. 2C and Fig. 2D . As an arrangement method, an ink-jet method is particularly preferable. The liquid droplets of the curable composition (A2) 203 are uniformly pressed on the substrate 201 opposed to the region where the concave portions are densely present on the mold 205, And are disposed on the opposing substrate 201 in a small manner. As a result, the remaining film to be described later can be controlled to have a uniform thickness regardless of the density of the pattern on the mold 205.

In the present invention, as described above, the droplets of the curable composition (A2) 203 disposed in the present step (second laminating step) are reduced by the effect of the Marangoni effect using the difference in surface energy (surface tension) And spread rapidly in the direction of the arrow 204 indicating the direction in which the droplet spreads (free spread) (Fig. 2d).

In the present invention, by setting the content of the component (d1) as the solvent in the curable composition (A1) 202 film to 10% by weight or less, the influence of the atmosphere control gas 307 (see FIG. 3B) The Marangoni effect is uniformly expressed, and a uniform pattern can be formed in the second shot area 305. [

&Lt; Mold contact process (3) >

Subsequently, as shown in Fig. 2E, the curable composition (A1) 202 and the curable composition (A2) 203, which are formed in the previous step (first and second laminating steps) The mold 205 having a circular pattern for transferring the pattern shape is brought into contact. As a result, a liquid partially mixed with the curable composition (A1) 202 and the curable composition (A2) 203 is filled in the concave portion of the fine pattern on the surface of the mold 205, 205) formed in a fine pattern.

As the mold 205, a mold 205 made of a light-transmitting material may be used in consideration of the next step (light irradiation step). Specific examples of the material of the mold 205 include a light-permeable resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor deposition film, a flexible film such as polydimethylsiloxane, desirable. However, when a light-transmitting resin is used as the material of the mold 205, it is necessary to select a resin that is not soluble in the components contained in the curable composition. Particularly preferably, the material of the mold 205 is made of quartz because the coefficient of thermal expansion is small and the pattern deformation is small.

The fine pattern that the mold 205 has on its surface preferably has a pattern height of 4 nm or more and 200 nm or less.

The lower the pattern height, the lower the releasing force of releasing the mold 205 from the cured film 207 of the resist in the mold releasing step, that is, the releasing force is low, and the resist pattern is torn along with the mold releasing, The number is small. The adjacent resist patterns are brought into contact with each other due to the elastic deformation of the resist pattern due to the impact at the time of detaching the mold 205 and the resist pattern may be adhered or broken. However, the pattern height may be about 2 times or less 2 or less), there is a high possibility that such problems can be avoided. On the other hand, if the pattern height is excessively low, the processing accuracy of the substrate 201 (the substrate to be processed) is low.

In the mold 205, curable compositions (A1), (A2), (A2), and (203) to improve the peelability of the surfaces of the curable compositions (A1) And the mold 205 may be subjected to a surface treatment before the main step. As a method of the surface treatment, a method of applying a releasing agent to the surface of the mold 205 to form a releasing agent layer can be mentioned. Examples of the releasing agent to be applied to the surface of the mold 205 include a silicone releasing agent, a fluorine releasing agent, a hydrocarbon releasing agent, a polyethylene releasing agent, a polypropylene releasing agent, a paraffin releasing agent, a montane releasing agent and a Carnauba releasing agent . For example, a commercially available coating type release system such as Optol (registered trademark) DSX manufactured by Daikin Industries, Ltd. can be suitably used. The release agent may be used alone or in combination of two or more. Of these, fluorine-based and hydrocarbon-based release agents are particularly preferable.

When the mold 205 is brought into contact with the curable compositions (A1) 202 and (A2) 203 in this step (mold contact step), the curable composition (A1) 202 ) And (A2) 203 are not particularly limited. The pressure may be from 0 MPa to 100 MPa. The pressure is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, still more preferably 0 MPa or more and 20 MPa or less.

In the present invention, since the free spread of the droplets of the curable composition (A2) 203 is progressing in the previous step (second lamination step), the spread of the curable composition (A2) 203 in this step is fast Is completed. In the liquid-droplet boundary region of the curable composition (A2) 203, the spread is finally completed and also the concentration of the curable composition (A1) 202 is high.

As described above, since the spreading and filling of the curable compositions (A1) 202 and (A2) 203 are completed quickly in this step, the mold 205 and the curable compositions A1, 202, It is possible to shorten the time for making the contact portion 203 contact. That is, it is one of the effects of the present invention that a large number of pattern forming steps can be completed in a short time and high productivity is obtained. The contact time is not particularly limited, but may be, for example, from 0.1 second to 600 seconds or less. The time is preferably 0.1 second or more and 3 seconds or less, and particularly preferably 0.1 second or more and 1 second or less. If it is shorter than 0.1 second, the spread and fill become insufficient, and defects called uncharged defects tend to be frequent.

The present step can be carried out under atmospheric pressure, under a reduced pressure atmosphere, or under an inert gas atmosphere. However, since it is possible to prevent the influence of oxygen or moisture on the curing reaction, . Specific examples of the inert gas that can be used in the present process in an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various kinds of freon gas, or a mixed gas thereof. When this step is carried out under an atmosphere of a specific gas including an atmosphere, the preferable pressure is 0.0001 to 10 atm. The inert gas is blown from the periphery of the mold 205 toward the gap between the mold 205 and the substrate 201.

The mold contact process may be performed under an atmosphere containing a condensable gas (hereinafter referred to as a &quot; condensable gas atmosphere &quot;). The condensable gas in this specification refers to the curable compositions (A1), (A2), (A2), and (203) in the concave portion of the fine pattern formed on the mold 205 and the gap between the mold 205 and the substrate 201 ), Which is condensed by the capillary pressure generated at the time of filling, and liquefied when the gas in the atmosphere is filled. Also, the condensable gas exists as a gas in the atmosphere before the curable compositions (A1) 202 and (A2) 203 and the mold 205 are in contact with each other in the mold-contacting process (see the partial enlargement of FIG.

When the mold contact process is performed in a condensable gas atmosphere, the gas filled in the concave portions of the fine patterns is liquefied by the capillary pressure generated by the curable compositions (A1), (A2), and (203) Therefore, the filling property is excellent. The condensable gas may be dissolved in the curable composition (A1) 202 and / or (A2) 203.

The boiling point of the condensable gas is not limited as long as it is not higher than the ambient temperature of the mold-contacting step, but it is preferably -10 캜 to 23 캜, more preferably 10 캜 to 23 캜. If it is in this range, the filling property is more excellent.

The vapor pressure at the atmospheric temperature of the mold-contacting step of the condensable gas is such that when the mold 205 is pressed with the curable composition (A1) 202 and (A2) 203 in the mold-contacting step, (A1) 202 and (A2) 203, it is preferably 0.1 to 0.4 MPa. If it is in this range, the filling property is more excellent. If the vapor pressure at the atmospheric temperature is larger than 0.4 MPa, the effect of bubble decay tends to be insufficient. On the other hand, if the vapor pressure at the atmospheric temperature is lower than 0.1 MPa, a reduced pressure is required, and the apparatus tends to be complicated.

The atmosphere temperature in the mold-contacting step is not particularly limited, but is preferably 20 占 폚 to 25 占 폚.

Specific examples of the condensable gas include chlorofluorocarbon (CFC) such as trichlorofluoromethane, fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), 1,1,1,3,3-penta Hydrofluorocarbons such as hydrofluorocarbon (HFC) such as fluoropropane (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP) and pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc) Ether (HFE), and the like.

Among them, 1,1,1,3,3-pentafluoropropane (having a vapor pressure of 0.14 MPa at 23 DEG C, a boiling point of 25 DEG C, 15 占 폚), trichlorofluoromethane (vapor pressure at 23 占 폚 0.1056 MPa, boiling point 24 占 폚) and pentafluoroethyl methyl ether are preferable. From the viewpoint of excellent safety, 1,1,1,3,3-pentafluoropropane is particularly preferable.

One type of condensable gas may be used alone, or two or more types may be mixed and used. These condensable gases may be used in combination with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. As the non-condensable gas to be mixed with the condensable gas, helium is preferable from the viewpoint of the filling ability. Helium can permeate through the mold 205. Therefore, the gas (condensable gas and helium) in the atmosphere together with the curable composition (A1) 202 and / or (A2) 203 is introduced into the concave portion of the fine pattern formed on the mold 205 in the mold- When charged, the condensable gas is liquefied and helium permeates the mold 205.

&Lt; Light irradiation step (4) >

Subsequently, as shown in FIG. 2F, irradiating light 206 is irradiated to the mixed layer in which the curable composition (A1) 202 and the curable composition (A2) 203 are partially mixed through the mold 205 do. More specifically, the curing composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is irradiated with the irradiation light 206 through the mold 205. As a result, the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is cured by the irradiation light 206 to be irradiated with the cured film 207).

Here, the irradiation light 206 irradiating the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205 is irradiated with the curable composition (A1) 202 and ) &Lt; / RTI &gt; Specifically, ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, X-ray, electron beam, or the like is preferably selected and used appropriately.

Of these, ultraviolet light is particularly preferable as the irradiation light 206. This is because a large number of compounds having sensitivity to ultraviolet light are commercially available as a curing aid (photopolymerization initiator). The chair as a light source for emitting ultraviolet light, for example, a high pressure mercury lamp, extra-high pressure mercury lamp, low pressure mercury lamps, Deep-UV lamps, carbon arc, a chemical lamp, a metal halide lamp, a xenon lamp, KrF excimer laser, ArF excimer laser, F ₂ excimer Laser, and the like, but ultra high-pressure mercury lamp is particularly preferable. The number of light sources used may be one or plural. The light irradiation may be performed on the entire surface of the curable composition (A1) 202 and / or (A2) 203 filled in the fine pattern of the mold 205, or may be performed only on a partial area.

The light irradiation may be performed intermittently a plurality of times over the entire area on the substrate 201, or may be continuously irradiated onto the entire area. It is also possible to irradiate a part of the area A in the first irradiation process and to check the area B which is different from the area A in the second irradiation process.

&Lt; Molding Process (5) >

Then, the mold 205 and the cured film 207 having a pattern shape are separated. 2G, the cured film 207 having the pattern shape and the mold 205 are separated from each other, and in the step (4) (light irradiation step), the mold 205 is separated from the mold 205, The cured film 207 having a pattern shape that becomes an inverted pattern of a fine pattern formed on the substrate 201 is obtained as a self-sustaining state. In addition, the cured film remains in the concave portion of the concavo-convex pattern of the cured film 207 having the pattern shape, and this film is referred to as a residual film 108 (see the partially enlarged portion in FIG.

When the mold contact process is performed in a condensable gas atmosphere, the pressure at the interface where the cured film 207 and the mold 205 are in contact with each other is lowered when the mold cavity 205 and the cured film 207 are separated in the mold release process The condensable gas is vaporized. Thereby, there is a tendency to exert the effect of reducing the releasing force, which is a force required for separating the cured film 207 from the mold 205. [

The method of separating the cured film 207 having a pattern shape from the mold 205 is not particularly limited as long as a part of the cured film 207 having a pattern shape at the time of separation is not physically damaged, It does not. For example, the substrate 201 (the substrate to be processed) may be fixed and the mold 205 may be moved away from the substrate 201 and peeled. Alternatively, the mold 205 may be fixed and the substrate 201 may be moved away from the mold 205 and peeled off. Alternatively, both of them may be pulled off in the opposite direction.

By the series of steps (manufacturing process) having the above-described steps (1) to (5), the desired concavo-convex pattern shape (pattern shape caused by the concave- convex shape of the mold 205) ) Can be obtained.

In the method of producing a film having a pattern shape according to the present embodiment, the curable composition (A1) 202 is laminated on the bulk of the surface of the substrate 201 in the step (1), and the steps (2) to (Shots) containing a plurality of repeating units can be repeated a plurality of times on the same substrate. The steps (1) to (5) may be repeated a plurality of times on the same substrate. A plurality of desired concavities and convexities are formed at desired positions on the substrate 201 (substrate to be processed) by repeating a plurality of repetition units (shots) including the steps (1) to (5) It is possible to obtain a cured film 207 having a pattern shape (pattern shape due to the concavo-convex shape of the mold 205). Further, the steps (1) to (5) may be performed collectively on the entire surface of the substrate 201.

Using the cured film 207 having the pattern shape obtained through the processes (1) to (5) as a mask, the substrate 201 (processed substrate) or the processed layer Can be processed into a pattern using processing means such as etching. Further, after the workpiece layer is further formed on the cured film 207 having a pattern shape, pattern transfer may be performed using processing means such as etching. In this manner, a circuit structure based on the pattern shape of the cured film 207 having a pattern shape can be formed on the substrate 201. Thus, a circuit board used in a semiconductor device or the like can be manufactured. In addition, by connecting this circuit board and a circuit control mechanism of a circuit board or the like, electronic devices such as a display, a camera, and a medical device can be formed. Examples of the semiconductor device include an LSI, a system LSI, a DRAM, an SDRAM, an RDRAM, a D-RDRAM, and a NAND flash.

The cured film 207 having a pattern shape obtained through the steps (1) to (5) is used as an optical member such as a diffraction grating or a polarizing plate (including the case of using as a member of an optical member) Parts can also be obtained. In this case, the optical component can be at least a substrate 201 and a cured film 207 having a pattern shape on the substrate 201.

A cured film 207 having a pattern shape is produced through the steps (1) to (5) using a quartz substrate as the substrate 201, pattern transfer is performed using processing means such as etching, A quartz replica (mold replica) of an imprint mold may be produced.

[Set of imprint pretreatment coating material (curable composition (A1)) and imprint resist (curable composition (A2)]]

Another aspect of the present invention is to provide an imprint pretreatment coating which promotes diffusion of a droplet component in a substrate surface direction by forming a liquid film to be pretreated on a substrate and applying a droplet containing the curable composition (A2) (Curable composition (A1)).

That is, the present invention is an imprint pretreatment coating material comprising a curable composition (A1) for forming a liquid film to be pretreated on a substrate and promoting diffusion of a liquid component in a direction of a substrate surface by applying droplets to the liquid film,

The content of the component (d1) as a solvent in the imprint pretreatment coating material is 90% by weight or more,

The content of the component (d1) as a solvent in the imprint pretreatment coating material at the time of applying the droplets is 10% by weight or less,

Wherein the surface tension of the component (d1) which is the solvent is lower than the surface tension of the composition of the component of the imprint pretreatment coating material excluding the component (d1) which is the solvent

&Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; imprint pretreatment coating material.

It is preferable that the surface tension of the imprint pretreatment coating is higher than the surface tension of the droplet imparted thereto.

In particular, it is preferable that the surface tension of the composition of the component of the imprint pretreatment coating material excluding the solvent is higher than the surface tension of the composition of the component of the imprint resist except for the solvent.

Thus, the liquid droplet is applied to the liquid film, whereby the diffusion of the liquid component in the substrate surface direction is promoted, and a suitable imprint can be realized.

In particular, it is preferable to be provided as a combination of an imprint resist and an imprint pretreatment coating material.

That is, the surface tension of the composition of the component of the imprint pre-treatment coating material other than the solvent is higher than the surface tension of the composition of the component of the imprint resist except the solvent, so that a suitable set of imprints is realized.

It is more preferable that the set of the combination of the surface tension of the composition of the component of the imprint pretreatment coating material other than the solvent and the surface tension of the composition of the component of the imprint resist except for the solvent is 1 mN / m or more and 25 mN / m or less.

Another aspect of the present invention is to provide a method of pretreating a suitable substrate for imprinting by coating an imprint pretreatment coating material on the substrate.

In addition, the present invention also includes a pattern formation method for forming a pattern on a substrate. By having the step of dropping the resist discontinuously on the substrate coated with the imprint pretreatment coating material, the diffusion of the resist component in the direction of the substrate surface is promoted, and the time required for the imprinting can be shortened.

<Examples>

Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited to the following Examples. In the following, "parts" and "%" used herein are by weight unless otherwise indicated.

(Example 1)

(1) Preparation of curable composition (A1-1)

The curable composition (A1-1), the component (b1), the component (c1) and the component (d1) shown below were blended and filtered with a filter made of a 0.2 mu m ultra high molecular weight polyethylene filter, Was prepared.

(1-1) Component (a1): 100 parts by weight in total

Trimethylolpropane triacrylate (Aldrich, abbreviated as TMPTA): 100 parts by weight

(1-2) Component (b1): 0 parts by weight in total

The component (b1) was not added.

(1-3) Component (c1): 0 parts by weight in total

Component (c1) was not added.

(1-4) Component (d1): 33000 parts by weight in total

Propylene glycol monomethyl ether acetate (manufactured by Tokyo Kasei Kogyo Co., abbreviated as PGMEA): 33000 parts by weight

(2) Preparation of curable composition (A2-1)

The curable composition (A2-1) of Example 1 was obtained by blending the components (a2), (b2), (c2) and (d2) shown below and filtering the mixture with a filter made of an ultra- Was prepared.

(2-1) Component (a2): 94 parts by weight in total

Isobornyl acrylate (trade name: IB-XA, available from Kyoeisha Chemical Co., Ltd.): 9 parts by weight

Benzyl acrylate (trade name: V # 160, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.): 38 parts by weight

Neopentyl glycol diacrylate (trade name: NP-A, manufactured by Kyoeisha Chemical Co., Ltd.): 47 parts by weight

(2-2) Component (b2): 3 parts by weight in total

Lucirin TPO (made by BASF): 3 parts by weight

(2-3) Component (c2): 0.8 parts by weight in total

Polyoxyethylene (13) stearyl ether (Kao Zeon, EMULGEN 320P): 0.8 parts by weight

(2-4) Component (d2): 0 parts by weight in total

The component (d2) was not added.

(3) Measurement of surface tension of the curable compositions (A1-1) and (A2-1)

(A1-1) except for the component (d1) which is a solvent at 25 deg. C was measured by a plate method using an automatic surface tension meter DY-300 (Kyowa Geimengagaku Co., Ltd.) The surface tension of the composition was measured to be 36.0 mN / m. The surface tension of the component (d1) as a solvent was measured and found to be 27.2 mN / m. The surface tension of the curable composition (A2-1) was measured and found to be 32.7 mN / m.

The measurement was carried out under the conditions of the number of times of measurement 5 times and the pre-wet immersion distance of the platinum plate 0.35 mm. The average value of the measured values from the second to the fifth times was taken as the surface tension, except for the first measured value.

(4) Consideration on the effect of free spread promotion

It is assumed that the residual ratio of the component (d1) as a solvent in the curable composition (A1-1) film is 0% by weight. The surface tension of the curable composition (A1-1) film is 36.0 mN / m, which is higher than 32.7 mN / m of the curable composition (A2-1) by 2 mN / m or more.

(5) Discussion on pattern uniformity in shot area

Similarly, it is assumed that the residual rate of the component (d1) as a solvent in the curable composition (A1-1) film is 0 wt%. Since the volatility of the component (a1) is low and the influence of the volatilization of the component (d1) which is a solvent is also slight, even in the portion where the atmosphere control gas is injected for the adjacent shots, the marangoni effect is uniformly expressed , It is possible to form a uniform pattern in the shot.

(Example 2)

(1) to (3) with respect to the curable compositions (A1) and (A2)

The same composition as in Example 1 was used.

(4) Consideration on the effect of free spread promotion

It is assumed that the residual ratio of the component (d1) as a solvent in the curable composition (A1-1) film is 10% by weight. In this case, the surface tension of the curable composition (A1-1) film is 35.1 mN / m, which is higher than 32.7 mN / m of the curable composition (A2-1) by 2 mN / m or more.

(5) Discussion on pattern uniformity in shot area

Similarly, it is assumed that the residual rate of the component (d1) as a solvent in the curable composition (A1-1) film is 10% by weight. Since the volatility of the component (a1) is low and the influence of the volatilization of the component (d1) which is a solvent is also slight, even in the portion where the atmosphere control gas is injected for the adjacent shots, the marangoni effect is uniformly expressed , It is possible to form a uniform pattern in the shot.

(Comparative Example 1)

(1) to (3) with respect to the curable compositions (A1) and (A2)

The same composition as in Example 1 was used.

(4) Consideration on the effect of free spread promotion

It is assumed that the residual ratio of the component (d1) as a solvent in the curable composition (A1-1) film is 20% by weight. In this case, since the surface tension of the curable composition (A1-1) film is 34.2 mN / m and the difference from 32.7 mN / m of the curable composition (A2-1) is 2 mN / m or less, the effect of promoting free spread is insufficient .

(5) Discussion on pattern uniformity in shot area

Similarly, it is assumed that the residual ratio of the component (d1) as a solvent in the curable composition (A1-1) film is 20% by weight. In the portion where the atmosphere control gas for the adjacent shot is sprayed, the volatilization of the component d1 as the solvent progresses, the surface tension of the curable composition A1-1 is increased, the Marangoni effect is exhibited, and the free spread promoting effect is obtained Loses. On the other hand, in the portion where the atmosphere control gas is not sprayed, the effect of promoting free spread is insufficient as described above. Therefore, uniformity of pattern formation in the shot is low.

(Comparative Example 2)

(1) to (3) with respect to the curable compositions (A1) and (A2)

The same composition as in Example 1 was used.

(4) Consideration on the effect of free spread promotion

It is assumed that the residual rate of the component (d1) as a solvent in the curable composition (A1-1) film is 50% by weight. In this case, the surface tension of the curable composition (A1-1) film is 31.6 mN / m, which is lower than 32.7 mN / m of the curable composition (A2-1), so that the effect of promoting free spread is insufficient.

(5) Discussion on pattern uniformity in shot area

Similarly, it is assumed that the residual ratio of the component (d1) as a solvent in the curable composition (A1-1) film is 50% by weight. In the portion where the atmosphere control gas for the adjacent shot is sprayed, the volatilization of the component d1 as the solvent progresses, the surface tension of the curable composition A1-1 is increased, the Marangoni effect is exhibited, and the free spread promoting effect is obtained Loses. On the other hand, in the portion where the atmosphere control gas is not sprayed, the effect of promoting free spread is insufficient as described above. Therefore, uniformity of pattern formation in the shot is low.

(Summary of Examples and Comparative Examples)

The compositions of Examples 1 to 2 and Comparative Examples 1 to 2 are shown in Tables 1 and 2, and the results are summarized in Table 3.

In Table 3, the evaluation of the effect of free spread promotion was made on the basis of a conventional optical nanoimprint process in which the curable composition (A1) was not applied. That is, if the speed is higher than that of the conventional optical nanoimprint process, the facilitating effect is called &quot; Yes &quot; The free spreads of Examples 1 and 2 are faster than those of Comparative Examples 1 and 2, and the free spread promotion effect is shown.

In Examples 1 and 2, the free spread is fast and the uniformity of pattern formation is good. In Comparative Examples 1 and 2, the free spread is slow, and the pattern formation is nonuniform within the shot.

As described above, the pattern forming method of the present embodiment has a high throughput and shows excellent uniformity.

This application claims priority from U.S. Patent Application No. 62 / 315,736, filed March 31, 2016, and U.S. Patent Application Serial No. 15 / 453,521, filed March 8, 2017, As part of the application.

101: substrate
102: Resist
104: arrow indicating the direction in which the droplet spreads
105: mold
106: irradiation light
107: Photocuring film having a pattern shape
108:
201: substrate (substrate to be processed)
202: Curable composition (A1)
203: Curable composition (A2)
204: arrow indicating the direction in which the droplet spreads
205: Mold
206: irradiation light
207:
301: substrate
302: Curable composition (A1)
303: Curable composition (A2)
304: first shot area
305: second shot area
306: irradiation light
307: atmosphere control gas
308: Mold
309: area where the atmosphere control gas is injected
310: The droplet of the curable composition (A2) dropped in the region (A1) in which the atmosphere control gas is injected

Claims (20)

A first lamination step (1) of laminating a layer containing a curable composition (A1) containing at least a polymerizable compound (a1) and a solvent component (d1)
A second lamination step (2) in which droplets of the curable composition (A2) containing at least a polymerizable compound (a2) are discretely dripped and laminated on the layer containing the curable composition (A1)
(3) sandwiching a mixed layer in which the curable composition (A1) and the curable composition (A2) are partially mixed between a mold having a pattern and the substrate,
A light irradiation step (4) for curing the mixed layer by irradiating light from the mold side,
(5) for separating the mold from the cured mixed layer,
In this order,
The content of the component (d1) as the solvent in the curable composition (A1) is 90% by weight or more,
, The content of the component (d1) as the solvent in the curing composition (A1) in the second laminating step (2) is 10% by weight or less,
Wherein the surface tension of the component (d1) which is the solvent is lower than the surface tension of the composition of the component of the curable composition (A1) except for the component (d1) which is the solvent. The positive resist composition according to claim 1, wherein the component (d1) as the solvent is a mixed solvent containing at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone, . The curable composition according to claim 1 or 2, wherein the surface tension of the composition of the component of the curable composition (A1) other than the component (d1) which is the solvent is higher than the surface tension of the composition of the component of the curable composition (A2) &Lt; / RTI &gt; The curable composition according to any one of claims 1 to 3, wherein the composition of the component of the curable composition (A1) other than the component (d1) which is the solvent has a viscosity of 1 mPa · s or more and 1000 mPa · s or less, Wherein the viscosity of the composition of the component of the curable composition (A2) other than the above-mentioned curable composition (A2) is 1 mPa 占 퐏 or more and 12 mPa 占 퐏 or less. The pattern forming method according to any one of claims 1 to 4, wherein the material of the surface of the mold is quartz. The pattern forming method according to any one of claims 1 to 5, wherein the mold-contacting step is performed in an atmosphere containing a condensable gas. The pattern forming method according to claim 6, wherein the second laminating step is performed in an atmosphere of a mixed gas of the condensable gas and the non-condensable gas. 8. The method of claim 7, wherein the non-condensable gas is helium. The pattern forming method according to any one of claims 6 to 8, wherein the condensable gas is 1,1,1,3,3-pentafluoropropane. A method for manufacturing a processed substrate, comprising the pattern forming method according to any one of claims 1 to 9. A method for manufacturing an optical component, comprising the pattern forming method according to any one of claims 1 to 9. A method for producing a quartz mold replica, comprising the pattern forming method according to any one of claims 1 to 9. 10. The pattern forming method according to any one of claims 1 to 9, wherein the pattern is a nano-sized concavo-convex pattern formed by the photo-cured product of the curable compositions (A1) and (A2). An imprint pretreatment coating material for forming a liquid film to be a pretreatment coating on a substrate and promoting diffusion of a liquid component in a substrate surface direction by applying a liquid droplet to the liquid film,
The content of the component (d1) as a solvent in the imprint pretreatment coating material is 90% by weight or more,
(D1) as the solvent in the imprint pretreatment coating material at the time of applying the droplets is 10% by weight or less,
Wherein the surface tension of the component (d1) which is the solvent is lower than the surface tension of the composition of the component of the imprint pretreatment coating material excluding the component (d1) which is the solvent. 15. The imprint pretreatment coating material according to claim 14, wherein the surface tension of the imprint pretreatment coating material is higher than the surface tension of the droplet imparted with the surface tension. 15. A set having an imprint pretreatment coating material according to claim 14 or 15 and an imprint resist for dropping onto a substrate coated with the imprint pretreatment coating material. The set according to claim 16, wherein the surface tension of the composition of the component of the imprint pretreatment coating material other than the solvent is higher than the surface tension of the composition of the component of the imprint resist except for the solvent. An imprint resist for use in the set according to claim 16 or claim 17. A pretreatment method for imprinting a curable composition on a substrate by coating the imprint pretreatment coating material according to claim 14 or 15 onto the substrate. A pattern forming method for forming a pattern on a substrate, comprising the step of discretely dripping a resist onto the substrate coated with the imprint pretreatment coating material according to claim 14 or 15.

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